CN109251293A - A kind of the triazines polyurethane carbon forming agent and its synthetic method of the side group containing furan nucleus - Google Patents

A kind of the triazines polyurethane carbon forming agent and its synthetic method of the side group containing furan nucleus Download PDF

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CN109251293A
CN109251293A CN201810796721.6A CN201810796721A CN109251293A CN 109251293 A CN109251293 A CN 109251293A CN 201810796721 A CN201810796721 A CN 201810796721A CN 109251293 A CN109251293 A CN 109251293A
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polyurethane
triazine
furan ring
side group
reaction
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CN109251293B (en
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李娟�
孙晋皓
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention discloses the triazines polyurethane carbon forming agent and its synthetic method of a kind of side group containing furan nucleus.The method comprises the steps of firstly, preparing side group containing furan nucleus and the diamines or diatomic alcohol compounds of triazine ring, then with after diisocyanate under the action of catalyst pre-polymerization, whole combinate form generating polyurethane material, the polyurethane material have excellent carbon-forming performance after addition chain extender.The method that the present invention prepares polyurethane carbon forming agent, side reaction is few, yield is high, it is easy to operate, the biology base furan compound of introducing can improve the degradability of polyurethane, and the introducing of furan nucleus and triazine ring can significantly improve polyurethane volume carbon-forming performance, obtain that good thermal stability, carbon-forming performance are excellent, the very high polyurethane carbon forming agent of remaining carbon, there is good development prospect in polymer Intumescent Retardant System.

Description

Triazine polyurethane charring agent containing furan ring side group and synthesis method thereof
Technical Field
The invention belongs to the technical field of polyurethane synthesis and modification, and particularly relates to a triazine polyurethane charring agent containing furan ring side groups and a synthesis method thereof.
Background
With the continuous development of society and the continuous progress of science and technology, polymer materials are more and more widely applied in the fields of transportation, electronic devices, building materials and the like which need fire prevention and flame retardance, so that the development and application of flame retardants are more and more emphasized. From the last 70 years to the present, the flame retardant has gradually changed from the point of only paying attention to flame retardance to green environmental protection, halogen-free low toxicity and high efficiency, and the traditional halogen flame retardant has gradually been replaced by a novel flame retardant means. Currently, the most widely studied flame retardants are mainly intumescent flame retardants, phosphorus-based flame retardants, phosphorus-nitrogen flame retardants, nano flame retardants, and some inorganic flame retardants.
The intumescent flame retardant is widely researched as a halogen-free environment-friendly flame retardant capable of effectively solving the dripping phenomenon in the combustion process of the polymer, and mainly comprises an acid source, a carbon source and a gas source. Among the three components, the carbon source is an important component, mainly plays a role in forming a carbon layer skeleton in the combustion and carbonization process, and is mainly composed of polyhydroxy small molecular compounds (such as pentaerythritol, sorbitol and the like), polyhydroxy polymers (polyurethane, polyvinyl alcohol, starch, cellulose and the like). Among a plurality of carbon forming agents, the polyurethane material is a common synthetic carbon source, has excellent carbon forming performance and good processing performance, can maintain good interface compatibility with a matrix, and reduces the loss of the mechanical property of the polymer. Meanwhile, the polyurethane is a good coating material and plays an important role in the preparation of the acid source-carbon source-air source integrated intumescent flame retardant at present. As a bio-based material, the furan ring-containing compounds have a great variety of functional groups (such as hydroxyl, amino, carboxyl, epoxy, acyl chloride, etc.), and are rich in chemical reactions, so that the furan ring-containing compounds are widely applied to polymerization reactions for preparing polyester PEF and derivative polyester, and are expected to replace traditional petrochemical-source plastics such as PET and PBT. Of course, the preparation of some heat-repairable materials (such as self-repairable epoxy resin) by utilizing the reversibility of diene addition reaction of furan rings and double-bond compounds is also an important direction for applying furan-containing compounds. However, at present, people introduce furan rings into an intumescent flame retardant system very rarely, and research focuses still on cyclic compounds containing high carbon and nitrogen contents such as benzene rings and triazine rings, but furan rings have excellent char-forming performance completely no inferior to benzene rings, and the furan rings can completely replace benzene ring compounds to play a role in an intumescent flame retardant carbon source. And the furan ring-containing compound is a sustainable material, is directly or indirectly derived from natural resources, is green and environment-friendly, can completely avoid pressure caused by shortage of petrochemical resources, reduces carbon emission, relieves pressure on the environment, and is a compound with good development prospect. The excellent char-forming properties of triazine rings are also well known. Therefore, the furan ring and the triazine ring are simultaneously introduced into the polyurethane material, and the polyurethane carbon source with excellent char-forming performance is believed to be prepared, so that the polyurethane carbon source has a good application prospect in the intumescent flame retardant.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an excellent polyurethane charring agent, which introduces furan rings and triazine rings in the preparation process of polyurethane and improves the charring performance of a polyurethane material.
The structural formula of the triazine polyurethane charring agent containing the furan ring side group is shown as follows:
wherein,is part of a diisocyanate group, R is-CH2O-、-CH2NH-、-CONH-、-COO-、 -NHCO-、-CH2S-、-CONHCH2-、R1 is-HNCH2CH2NH-、 -HNCH2CH2CH2CH2NH-、-NHPh-CH2-PhNH-、-NHPh-SO-PhNH-、-NHPhNH-、-NHCH2-Ph-CH2NH-、 -OCH2CH2O-、-OCH2CH2CH2CH2O-, -phenolphthalein-, -NH-Ph-O-, -COOCH2CH2CH2CH2O-, or a combination thereof.
The invention also aims to provide a synthesis method of the triazine polyurethane charring agent containing the furan ring side group, firstly, diamine or diol compound containing the furan ring side group and the triazine ring is prepared, then, the diamine or diol compound and diisocyanate are prepolymerized under the action of a catalyst, and finally, a chain extender is added to form a polyurethane material, wherein the polyurethane material has excellent charring performance, and the synthesis method specifically comprises the following steps:
step 1) completely dissolving triazine compounds in an organic solvent 1, slowly dropwise adding an organic solvent 1 solution containing furan ring compounds and acid-binding agents at-20-30 ℃ under the protection of nitrogen, and continuously reacting for 0.5-8 h at-20-30 ℃ after dropwise adding.
The molar ratio of the triazine compound, the furan ring-containing compound and the acid-binding agent is 1 (0.5-6) to (1-8), and preferably 1 (1-3) to (1-4).
Preferably, the dropping condition in the step 1) is nitrogen protection at the temperature of-20 ℃, the dropping time is controlled to be 0.5-2 h, and the reaction is continuously carried out for 2-6 h at the temperature of-20 ℃.
The triazine compound is one or more of cyanuric chloride, cyanuric acid, trithiocyanuric acid and derivatives thereof, and preferably cyanuric chloride.
The compound containing the furan nucleus is one or more of furan methanol, furan formaldehyde, furan methylamine, furan formic acid, acetic acid furan methyl ester, furfuryl mercaptan and glycidyl furfuryl ether, preferably one of furan methanol, furan methylamine, furfuryl mercaptan and glycidyl furfuryl ether, and further preferably one of furan methanol and furan methylamine.
The acid-binding agent is at least one of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium ethoxide, ethylenediamine, triethylamine and pyridine, and preferably one of triethylamine and pyridine.
The organic solvent 1 is one or more mixed solvents of tetrahydrofuran, acetonitrile, 1, 4-dioxane, acetone, trichloromethane, dichloromethane, dichloroethane, petroleum ether, hexane, cyclohexane, toluene and xylene, preferably one of acetonitrile and 1, 4-dioxane, and more preferably 1, 4-dioxane.
Step 2) completely dissolving diamine or dihydric alcohol and an acid-binding agent in an organic solvent 1, slowly dripping the solution in the step 1) at 0-80 ℃, continuing to react for 0.5-8 h after dripping is finished, and raising the temperature to 80-120 ℃ again to continue to react for 0.5-8 h; after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a triazine polyurethane dihydric alcohol or diamine monomer containing furan ring side groups;
the molar ratio of the diamine or the dihydric alcohol, the acid-binding agent and the triazine compound in the step 1) is (0.5-4): 1-6): 1, and preferably (1-4): 1.
Preferably, the dropping condition is under the protection of nitrogen at 30-80 ℃, the dropping time is controlled to be 0.5-2 h, and the reaction is continued to be carried out for 2-8 h at 80-120 ℃.
The diamine or diol is one or more of aliphatic or aromatic diamine or diol such as phenolphthalein, ethylene glycol, butanediol, ethylenediamine, butanediamine, 4-diaminodiphenylmethane and 4, 4-diaminodiphenylsulfone, and is preferably common diol or diamine such as phenolphthalein, butanediol, 4-diaminodiphenylmethane and ethylenediamine.
The acid-binding agent is at least one of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium ethoxide, ethylenediamine, triethylamine and pyridine, and preferably one of triethylamine and pyridine.
Step 3) completely dissolving the triazine polyurethane dihydric alcohol or diamine monomer containing the furan ring side group obtained in the step 2) after completely removing water and diisocyanate in the organic solvent 2 after removing water, mechanically stirring uniformly, adding a catalyst and then carrying out prepolymerization; and (3) adding a dihydric alcohol chain extender, continuing the reaction, detecting the reaction progress by using an infrared spectrometer, and volatilizing the solvent after the reaction is finished to obtain a polyurethane product.
The molar ratio of the furan ring-containing side group triazine dihydric alcohol or diamine to the diisocyanate to the dihydric alcohol chain extender is (0.8-1.5) to 1 (0.05-0.5);
the diisocyanate is one or more mixtures of diisocyanates with the molecular weight of less than 300 g/mol;
the catalyst is an organic tin compound;
the dihydric alcohol chain extender is at least one of propylene glycol and butanediol or a mixed chain extender of the dihydric alcohol chain extender and other polyhydric alcohol compounds, and is preferably common dihydric alcohol such as propylene glycol and butanediol.
The organic solvent 2 is at least one of N, N-dimethylformamide, dimethyl sulfoxide, toluene, xylene and 1, 2-dichloroethane, and is preferably one of N, N-dimethylformamide and toluene.
The triazine polyurethane charring agent containing the furan ring side group introduces the bio-based furan compound and the triazine ring into the polyurethane, so that the charring performance of the synthesized polyurethane can be obviously improved, the introduced bio-based compound can improve the biodegradability of the polyurethane and reduce the burden on the environment, and meanwhile, the furan ring on the side chain and other functional groups carried by the furan ring also provide possibility for the reactivity and the functionalization of the polyurethane.
Compared with the prior art, the invention has the following advantages:
firstly, successfully preparing triazine polyurethane dihydric alcohol or diamine monomer containing furan ring side group by nuclear magnetic hydrogen spectrum1HNMR), infrared spectrometer (FT-IR), etc. verified the successful preparation of the monomer. Synthesizing the triazine polyurethane containing furan ring side group by the traditional polyurethane polymerization technology, and performing nuclear magnetic hydrogen spectrum (A), (B), (C) and (C)1HNMR), infrared spectrometer (FT-IR) and the like verify the successful preparation of polyurethane, and the polyurethane is involuted by a Thermal Gravimetric Analyzer (TGA)Tests on the thermal stability and the residual carbon content of the synthesized polyurethane show that the synthesized polyurethane has good thermal stability and high residual carbon content, and can be applied to the expansion flame retardance of different polymer systems.
The preparation of the polyurethane charring agent has the advantages of less side reaction in each step, high yield and simple and convenient operation, introduces the bio-based furan compound in the synthesis process, reduces the tolerance to petroleum-based products in the synthesis process, reduces the synthesis cost and improves the degradability of polyurethane.
According to the invention, furan rings and triazine rings with excellent char forming performance are introduced into polyurethane, so that the polyurethane char forming agent with good thermal stability, excellent char forming performance and high carbon residue is obtained, and the polyurethane char forming agent has a good development prospect in a polymer expansion flame-retardant system.
Drawings
FIG. 1 shows example 4 of a triazine urethane diol or diamine containing pendant furan ring groups1HNMR spectrogram;
FIG. 2 is a schematic representation of example 4 triazine urethane char-forming agents containing pendant furan ring groups1HNMR spectrogram;
FIG. 3 is an infrared spectrum of the triazine urethane diol or diamine containing pendant furan ring groups and the triazine urethane char-forming agent of example 4;
FIG. 4 is a thermogravimetric analysis (TGA) curve of triazine polyurethane diol or diamine monomer containing furan ring side group under nitrogen in example 1 and example 4;
FIG. 5 is a thermogravimetric analysis (TGA) curve under nitrogen for triazine polyurethane charring agent containing furan ring pendant group in example 1 and example 4.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The polypropylene is of a commercially available general grade, is preferably an extruded or injection molded type, has a melting point of 160-175 ℃, a melt index of 2-15 g/10min, and is further preferably Chinese winnowing F401.
The polymerization degree n of the ammonium polyphosphate is more than 1500, and preferably, the ammonium polyphosphate is Chinese Qingyuan Puseff phosphorus chemical EPER-231.
The following examples used 4, 4-diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) molecular weights of less than 300 g/mol.
Example 1:
completely dissolving 1mol of cyanuric chloride in 300mL of 1, 4-dioxane in a 1000mL three-necked bottle, slowly dripping 100mL of 1, 4-dioxane solution in which 1mol of furylamine and 1mol of triethylamine are dissolved in the three-necked bottle under the protection of ice salt bath and nitrogen, controlling the dripping time to be 2h, and continuing to react for 2h in the ice salt bath after the dripping is finished.
At room temperature, 100mL of 1, 4-dioxane solution containing 2mol of ethylenediamine and 2mol of triethylamine was slowly added dropwise, and after the dropwise addition, the temperature was raised to 110 ℃ to continue the reaction for 8 hours. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a product 1 for later use.
Completely dissolving 1mol of completely dehydrated product 1 and 1mol of 4, 4-diphenylmethane diisocyanate (MDI) in dehydrated 400mLN, N-dimethylformamide, mechanically stirring uniformly, adding 20 drops of dibutyltin dilaurate serving as an organic tin catalyst, and prepolymerizing for 4 hours at the temperature of 60 ℃ under the protection of nitrogen; titrating the residual quantity of isocyanate by using an acetone-di-n-butylamine method, adding a proper amount of 0.40mol of 1, 4-butanediol as a chain extender, heating to 80 ℃, continuing the reaction, detecting the content of isocyanate by using an infrared spectrometer, and volatilizing a solvent after the reaction is finished to obtain a polyurethane product. The structural formulas of the product 1 of example 1 and the polyurethane product 1 are shown as follows:
example 2:
completely dissolving 1mol of cyanuric chloride in 400mL of acetonitrile in a 1000mL three-necked bottle, slowly dripping 100mL of acetonitrile solution in which 1mol of furylamine and 1mol of pyridine are dissolved in the acetonitrile in an ice salt bath and under the protection of nitrogen, controlling the dripping time to be 2h, and continuing to react for 2h in the ice salt bath after the dripping is finished.
At room temperature, slowly dripping 100mL of acetonitrile solution dissolved with 2mol of phenolphthalein and 2.6mol of pyridine into the solution, and after the dripping is finished, heating to 110 ℃ to continue the reaction for 8 h. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a product 2 for later use.
Completely dissolving 1mol of completely dehydrated product 2 and 1mol of Hexamethylene Diisocyanate (HDI) in dehydrated 400mL of toluene, mechanically stirring uniformly, adding 20 drops of an organotin catalyst dibutyltin dilaurate, and carrying out prepolymerization for 4h at 60 ℃ under the protection of nitrogen; titrating the residual quantity of isocyanate by using an acetone-di-n-butylamine method, adding a proper amount of 0.46mol of 1, 4-butanediol as a chain extender, heating to 80 ℃, continuing the reaction, detecting the content of isocyanate by using an infrared spectrometer, and volatilizing the solvent after the reaction is finished to obtain a polyurethane product. The structural formulas of the product 2 of example 2 and the polyurethane product 2 are shown as follows:
example 3:
completely dissolving 1mol of cyanuric chloride in 300mL of 1, 4-dioxane in a 1000mL three-necked bottle, slowly dripping 100mL of 1, 4-dioxane solution in which 1mol of furfuryl alcohol and 1mol of pyridine are dissolved in an ice salt bath under the protection of nitrogen, controlling the dripping time to be 2h, and continuing to react for 2h in the ice salt bath after the dripping is finished.
At room temperature, 100mL of 1, 4-dioxane solution containing 2mol of 4, 4-diaminodiphenylmethane (DDM) and 2mol of pyridine dissolved therein was slowly dropped, and after the dropping was completed, the temperature was raised to 110 ℃ to continue the reaction for 8 hours. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a product 3 for later use.
Completely dissolving 1mol of the product 3 completely dehydrated and 1mol of isophorone diisocyanate (IPDI) in 500mLN, N-dimethylformamide dehydrated, mechanically stirring uniformly, adding 20 drops of dibutyltin dilaurate serving as an organic tin catalyst, and prepolymerizing for 4 hours at 60 ℃ under the protection of nitrogen; titrating the residual quantity of isocyanate by using an acetone-di-n-butylamine method, adding a proper amount of 0.36mol of 1, 4-butanediol as a chain extender, heating to 80 ℃, continuing the reaction, detecting the content of isocyanate by using an infrared spectrometer, and volatilizing a solvent after the reaction is finished to obtain a polyurethane product. The structural formulas of the product 3 of example 3 and the polyurethane product 3 are shown as follows:
example 4:
completely dissolving 1mol of cyanuric chloride in 300mL of 1, 4-dioxane in a 1000mL three-necked bottle, slowly dripping 100mL of 1, 4-dioxane solution in which 1mol of furylamine and 1.6mol of triethylamine are dissolved in the solution under the protection of ice salt bath and nitrogen, controlling the dripping time to be 2h, and continuing to react for 2h in the ice salt bath after the dripping is finished.
At room temperature, 100mL of 1, 4-dioxane solution containing 2mol of 4, 4-diaminodiphenylmethane (DDM) and 2.4mol of triethylamine was slowly dropped into the solution, and after the dropping, the temperature was raised to 110 ℃ to continue the reaction for 8 hours. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a product 4 for later use.
Completely dissolving 1mol of completely dehydrated product 4 and 1mol of diphenylmethane diisocyanate (MDI) in dehydrated 400mLN, N-dimethylformamide, mechanically stirring uniformly, adding 20 drops of organic tin catalyst dibutyltin dilaurate, and prepolymerizing for 4h at 60 ℃ under the protection of nitrogen; titrating the residual quantity of isocyanate by using an acetone-di-n-butylamine method, adding a proper amount of 0.40mol of 1, 4-butanediol as a chain extender, heating to 80 ℃, continuing the reaction, detecting the content of isocyanate by using an infrared spectrometer, and volatilizing a solvent after the reaction is finished to obtain a polyurethane product. The structural formulas of the product 4 of example 4 and the polyurethane product 4 are shown as follows:
example 5:
completely dissolving 1mol of cyanuric chloride in 300mL of 1, 4-dioxane in a 1000mL three-necked bottle, slowly dripping 100mL of 1, 4-dioxane solution in which 1mol of furylamine and 1.2mol of pyridine are dissolved in the three-necked bottle under the protection of ice salt bath and nitrogen, controlling the dripping time to be 2h, and continuing to react for 2h in the ice salt bath after the dripping is finished.
At room temperature, 100mL of 1, 4-dioxane solution containing 2mol of butanediamine and 3.2mol of pyridine was slowly added dropwise, and after the dropwise addition was completed, the temperature was raised to 90 ℃ to continue the reaction for 4 hours. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a product 5 for later use.
Completely dissolving 1mol of completely dehydrated product 5 and 1mol of diphenylmethane diisocyanate (MDI) in dehydrated toluene, mechanically stirring uniformly, adding 20 drops of dibutyltin dilaurate serving as an organic tin catalyst, and carrying out prepolymerization for 4 hours at 60 ℃ under the protection of nitrogen; titrating the residual quantity of isocyanate by using an acetone-di-n-butylamine method, adding a proper amount of 0.32mol of 1, 4-butanediol as a chain extender, heating to 80 ℃, continuing the reaction, detecting the content of isocyanate by using an infrared spectrometer, and volatilizing a solvent after the reaction is finished to obtain a polyurethane product. The structural formulas of the product 5 of example 5 and the polyurethane product 5 are shown as follows:
example 6:
completely dissolving 1mol of cyanuric chloride in 400mL of acetonitrile in a 1000mL three-necked bottle, slowly dripping 100mL of acetonitrile solution dissolved with 4mol of furylamine and 1.5mol of pyridine in the acetonitrile in an ice salt bath under the protection of nitrogen, controlling the dripping time to be 2h, and reacting at room temperature for 2h after the dripping is finished.
At room temperature, 100mL of acetonitrile solution in which 2mol of butanediol and 2.5mol of pyridine were dissolved was slowly dropped thereinto, and after the dropping was completed, the temperature was raised to 90 ℃ to continue the reaction for 8 hours. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a product 6 for later use.
Completely dissolving 1mol of completely dehydrated product 6 and 1mol of diphenylmethane diisocyanate (MDI) in dehydrated 400mLN, N-dimethylformamide, mechanically stirring uniformly, adding 20 drops of dibutyltin dilaurate serving as an organic tin catalyst, and prepolymerizing for 4 hours at 60 ℃ under the protection of nitrogen; titrating the residual quantity of isocyanate by using an acetone-di-n-butylamine method, adding a proper amount of 0.47mol of 1, 4-propylene glycol as a chain extender, heating to 80 ℃, continuing the reaction, detecting the content of isocyanate by using an infrared spectrometer, and volatilizing a solvent after the reaction is finished to obtain a polyurethane product. The structural formulas of the product 6 of example 6 and the polyurethane product 6 are shown as follows:
example 7:
completely dissolving 1mol of cyanuric chloride in 400mL of acetonitrile in a 1000mL three-necked bottle, slowly dripping 100mL of acetonitrile solution in which 1mol of furylamine and 1.0mol of triethylamine are dissolved in the three-necked bottle under the protection of ice salt bath and nitrogen, controlling the dripping time to be 2h, and reacting at room temperature for 4h after the dripping is finished.
At room temperature, slowly dripping 100mL of acetonitrile solution dissolved with 2mol of butanediamine and 2.4mol of triethylamine into the solution, and after the dripping is finished, heating to 90 ℃ to continue the reaction for 8 h. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a product 7 for later use.
Completely dissolving 1mol of completely dehydrated product 7 and 1mol of Hexamethylene Diisocyanate (HDI) in dehydrated 400mLN, N-dimethylformamide, mechanically stirring uniformly, adding 20 drops of an organotin catalyst dibutyltin dilaurate, and prepolymerizing for 4 hours at 60 ℃ under the protection of nitrogen; titrating the residual quantity of isocyanate by using an acetone-di-n-butylamine method, adding a proper amount of 0.51mol of 1, 4-butanediol as a chain extender, heating to 80 ℃, continuing the reaction, detecting the content of isocyanate by using an infrared spectrometer, and volatilizing a solvent after the reaction is finished to obtain a polyurethane product. The structural formulas of the product 7 of example 7 and the polyurethane product 7 are shown below:
example 8:
completely dissolving 1mol of cyanuric chloride in 400mL of acetonitrile in a 1000mL three-necked bottle, slowly dripping 100mL of acetonitrile solution dissolved with 1mol of furfuryl alcohol and 1.6mol of triethylamine in an ice salt bath under the protection of nitrogen, controlling the dripping time to be 2h, and reacting at room temperature for 4h after the dripping is finished.
At room temperature, slowly dropping 100mL of acetonitrile solution containing 2mol of butanediol and 2.6mol of triethylamine, after dropping, heating to 90 ℃ and continuing reaction for 8 h. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a product 8 for later use.
Completely dissolving 1mol of the completely dehydrated product 8 and 1mol of diphenylmethane diisocyanate (MDI) in dehydrated 400mLN, N-dimethylformamide, mechanically stirring uniformly, adding 20 drops of an organotin catalyst dibutyltin dilaurate, and prepolymerizing for 4 hours at 60 ℃ under the protection of nitrogen; titrating the residual quantity of isocyanate by using an acetone-di-n-butylamine method, adding a proper amount of 0.42mol of 1, 4-butanediol as a chain extender, heating to 80 ℃, continuing the reaction, detecting the content of isocyanate by using an infrared spectrometer, and volatilizing a solvent after the reaction is finished to obtain a polyurethane product. The structural formulas of the product 8 of example 8 and the polyurethane product 8 are shown below:
example 9:
completely dissolving 1mol of cyanuric acid in 400mL of acetone in a 1000mL three-necked bottle, slowly dripping acetone solution dissolved with 6mol of furylamine and 3mol of pyridine into the cyanuric acid in the presence of nitrogen at 30 ℃, controlling the dripping time to be 2 hours, and reacting at 30 ℃ for 2 hours after the dripping is finished.
At 80 ℃, slowly dripping 100mL of acetone solution dissolved with 2.4mol of 4, 4-diaminodiphenyl sulfone and 2.4mol of pyridine into the mixture, and after finishing dripping, heating to 120 ℃ to continue reacting for 0.5 h. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a product 9 for later use.
Completely dissolving 1mol of the completely dehydrated product 9 and 1mol of diphenylmethane diisocyanate (MDI) in dehydrated toluene, mechanically stirring uniformly, adding dibutyltin dilaurate, and prepolymerizing for 4h at 60 ℃ under the protection of nitrogen; titrating the residual quantity of isocyanate by using an acetone-di-n-butylamine method, adding 0.5mol of propylene glycol as a chain extender, heating to 80 ℃, continuing to react, detecting the content of the isocyanic acid radical by using an infrared spectrometer, and volatilizing a solvent after the reaction is finished to obtain a polyurethane product. The structural formulas of the product 9 of example 9 and the polyurethane product 9 are shown as follows:
example 10:
completely dissolving 1mol of trithiocyanuric acid in 400mL of trichloromethane in a 1000mL three-necked bottle, slowly dripping 100mL of trichloromethane solution dissolved with 1mol of glycidyl furfuryl ether and 1.5mol of pyridine into the trichloromethane solution at 20 ℃ under the protection of nitrogen, controlling the dripping time to be 1h, and reacting for 2h at 20 ℃ after the dripping is finished.
Slowly dripping the chloroform solution dissolved with 2mol of butanediol and 2.2mol of pyridine into the chloroform solution at room temperature, and after the dripping is finished, heating to 100 ℃ to continue the reaction for 3 hours. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a product for later use.
Completely dissolving the 0.9mol of completely dehydrated product and 1mol of diphenylmethane diisocyanate (MDI) in dehydrated toluene, mechanically stirring uniformly, adding dibutyltin dilaurate, and prepolymerizing for 4h at 60 ℃ under the protection of nitrogen; titrating the residual quantity of isocyanate by using an acetone-di-n-butylamine method, adding 0.4mol of 1, 4-propylene glycol as a chain extender, heating to 80 ℃, continuing the reaction, detecting the content of the isocyanic acid radical by using an infrared spectrometer, and volatilizing a solvent after the reaction is finished to obtain a polyurethane product. The structural formulas of the product 10 of example 10 and the polyurethane product 10 are shown below:
example 11:
in a 1000mL three-necked bottle, 1mol of cyanuric chloride is completely dissolved in dichloromethane, and a dichloromethane solution dissolved with 2mol of furfuryl mercaptan and 3mol of sodium carbonate is slowly dripped into the cyanuric chloride under the protection of nitrogen at 10 ℃, the dripping time is controlled to be 1h, and after the dripping is finished, the cyanuric chloride reacts for 4h at 10 ℃.
Slowly dripping dichloromethane solution dissolved with 2mol of butanediol and 3mol of sodium carbonate into the solution at room temperature, and after the dripping is finished, heating to 110 ℃ to continue the reaction for 5 hours. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a product for later use.
Completely dissolving 1mol of the completely dehydrated product and 1mol of diphenylmethane diisocyanate (MDI) in dehydrated xylene, mechanically stirring uniformly, adding dibutyltin dilaurate, and prepolymerizing for 4h at 60 ℃ under the protection of nitrogen; titrating the residual quantity of isocyanate by using an acetone-di-n-butylamine method, adding 0.3mol of 1, 4-butanediol as a chain extender, heating to 80 ℃, continuing to react, detecting the content of isocyanate by using an infrared spectrometer, and volatilizing a solvent after the reaction is finished to obtain a polyurethane product. The structural formulas of the product 11 of example 11 and the polyurethane product 11 are shown below:
example 12:
completely dissolving 1mol of cyanuric acid in 400mL of acetonitrile in a 250mL three-necked bottle, slowly dripping 100mL of acetonitrile solution dissolved with 1mol of glycidyl furfuryl ether in the acetonitrile in an ice salt bath under the protection of nitrogen, controlling the dripping time to be 2h, and reacting at room temperature for 4h after the dripping is finished.
At room temperature, 100mL of acetonitrile solution in which 2.5mol of butanediol was dissolved was slowly dropped thereinto, and after the dropping was completed, the temperature was raised to 90 ℃ to continue the reaction for 8 hours. And after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a product for later use.
Completely dissolving 1mol of the completely dehydrated product 1 and 1mol of diphenylmethane diisocyanate (MDI) in the dehydrated N, N-dimethylformamide, mechanically stirring uniformly, adding dibutyltin dilaurate, and prepolymerizing for 4h at 60 ℃ under the protection of nitrogen; titrating the residual quantity of isocyanate by using an acetone-di-n-butylamine method, adding 0.4mol of 1, 4-butanediol as a chain extender, heating to 80 ℃, continuing to react, detecting the content of isocyanate by using an infrared spectrometer, and volatilizing a solvent after the reaction is finished to obtain a polyurethane product. The structural formulas of the product 12 of example 12 and the polyurethane product 12 are shown below:
as shown in fig. 1, the nuclear magnetic hydrogen spectra in fig. 1 and fig. 2 effectively demonstrate that the successful preparation of the polyurethane containing the furan ring diamine or diol monomer and the furan ring side group, the shift of each group of peaks and the peak area ratio substantially conform to the theoretical data; the ir spectrum in fig. 3 further demonstrates that the desired monomer and polyurethane products are obtained with no polyurethane residue; as is obvious from the thermal degradation curve (shown in figures 4 and 5) under the nitrogen atmosphere, the prepared triazine polyurethane charring agent containing the furan ring side group has good thermal stability, the initial decomposition temperature is about 300 ℃, and the residual carbon content at 600 ℃ under the nitrogen atmosphere is more than 50%. In general, the prepared polyurethane is a good char-forming agent and has good application prospect in an expansion flame-retardant system.
Application example 1
Weighing the following raw materials by weight:
85Kg of polypropylene (PP, China Yankee petrochemical, F401), 11.25Kg of ammonium polyphosphate (APP, Pulseff phosphorus chemical company, EPER-231), and 3.75Kg of furan ring-containing polyurethane prepared in example 4;
the preparation method of the flame-retardant composite material comprises the following steps:
polypropylene and furan ring-containing polyurethane prepared in example 4 were dried at 80 ℃ for 8 h. And (3) mixing in a high-speed blender, adding into a double-screw extruder, melting and blending (the screw temperature is 190-220 ℃), cooling and granulating to obtain the polypropylene flame-retardant composite material. The length-diameter ratio of the screw of the selected double-screw extruder is 40: 1.
Application example 2
Weighing the following raw materials by weight:
85Kg of polypropylene (PP, China Yankee petrochemical, F401), 10Kg of ammonium polyphosphate (APP, Pulseff phosphorus chemical company, EPER-231), and 5Kg of furan ring-containing polyurethane prepared in example 4;
the preparation is as described in application example 1.
Application example 3
Weighing the following raw materials by weight:
80Kg of polypropylene (PP, China Yankee petrochemical, F401), 13.33Kg of ammonium polyphosphate (APP, Pulseff phosphorus chemical company, EPER-231), and 6.67Kg of furan ring-containing polyurethane prepared in example 4;
the preparation is as described in application example 1.
Application example 4
Weighing the following raw materials by weight:
80Kg of polypropylene (PP, China Yankee petrochemical, F401), 15Kg of ammonium polyphosphate (APP, Pulseff phosphorus chemical company, EPER-231), and 5Kg of furan ring-containing polyurethane prepared in example 4;
the preparation is as described in application example 1.
Comparative example 1
Weighing the following raw materials by weight:
100Kg of polypropylene (PP, Chinese raisin, F401);
the preparation is as described in application example 1.
Comparative example 2
Weighing the following raw materials by weight:
80Kg of polypropylene (PP, China Yangzhiti petrochemical, F401) and 20Kg of ammonium polyphosphate (APP, Pulseff phosphorus chemical industry Co., EPER-231);
the preparation is as described in application example 1.
The polypropylene and the flame-retardant composite material thereof obtained by applying the examples 1-4, the comparative examples 1 and the comparative examples 2 are injection molded into a standard vertical burning (UL-94) sample strip, a Limiting Oxygen Index (LOI) sample strip and a tensile sample strip, wherein the injection molding temperature is 190-220 ℃, the injection pressure is 70-90 MPa, and the pressure maintaining pressure is 45 MPa. The test results of the burning properties and oxygen index were as shown in Table 1 according to ASTM D3801 and ASTM D2863-97, and NC means no grade.
TABLE 1
As can be seen from Table 1, by comparing application examples 1-4 with comparative example 1 and comparative example 2, the prepared furan ring-containing polyurethane can effectively replace the traditional polyhydroxy compound (such as pentaerythritol, starch and the like) char forming agent to obtain a relatively excellent flame retardant effect in polypropylene, when the ratio of APP to furan ring-containing polyurethane is 2:1 and the addition amount reaches 25%, the polypropylene can pass the V1 grade, the oxygen index is remarkably increased to 28.3%, which indicates that the prepared furan ring-containing polyurethane can reduce the content of APP to a certain extent, and the prepared furan ring-containing polyurethane can replace the traditional char forming agent such as pentaerythritol to obtain a relatively outstanding effect in an intumescent flame retardant system.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as the requirements of the present invention are met.

Claims (10)

1. A triazine polyurethane charring agent containing furan ring side group is characterized in that the structural formula is as follows:
wherein,is part of a diisocyanate group, R is-CH2O-、-CH2NH-、-CONH-、-COO-、-NHCO-、-CH2S-、-CONHCH2-、R1 is-HNCH2CH2NH-、-HNCH2CH2CH2CH2NH-、-NHPh-CH2-PhNH-、-NHPh-SO-PhNH-、-NHPhNH-、-NHCH2-Ph-CH2NH-、-OCH2CH2O-、-OCH2CH2CH2CH2O-, -phenolphthalein-, -NH-Ph-O-, -COOCH2CH2CH2CH2O-, or a combination thereof.
2. A synthetic method of a triazine polyurethane charring agent containing a furan ring side group is characterized by comprising the following steps:
step 1), completely dissolving triazine compounds in an organic solvent 1, slowly dropwise adding an organic solvent 1 solution containing furan ring compounds and acid-binding agents at-20-30 ℃ under the protection of nitrogen, and continuously reacting at-20-30 ℃ for 0.5-8 h after dropwise adding;
step 2), after completely dissolving diamine or dihydric alcohol and an acid-binding agent in the organic solvent 1, slowly dripping the solution in the step 1) at 0-80 ℃, continuing to react for 0.5-8 h after dripping is finished, and raising the temperature to 80-120 ℃ again to continue to react for 0.5-8 h; after the reaction is finished, carrying out suction filtration, carrying out rotary evaporation on the filtrate to obtain solid powder, washing the solid powder for 5 times by using deionized water, and carrying out vacuum drying to obtain a triazine polyurethane dihydric alcohol or diamine monomer containing furan ring side groups;
step 3), completely dissolving the triazine polyurethane dihydric alcohol or diamine monomer containing the furan ring side group obtained in the step 2) after completely removing water and diisocyanate in the organic solvent 2 after removing water, mechanically stirring uniformly, adding a catalyst and then carrying out prepolymerization; and (3) adding a dihydric alcohol chain extender, continuing the reaction, detecting the reaction progress by using an infrared spectrometer, and volatilizing the solvent after the reaction is finished to obtain a polyurethane product.
3. The method for synthesizing the triazine polyurethane charring agent containing the furan ring side group as claimed in claim 2, wherein the molar ratio of the triazine compound, the furan ring containing compound and the acid binding agent in the step 1) is 1 (0.5-6) to (1-8).
4. The method for synthesizing the triazine polyurethane charring agent containing the furan ring side group as claimed in claim 2, wherein the molar ratio of the diamine or the diol and the acid-binding agent in the step 2) to the triazine compound in the step 1) is (0.5-4): 1-6): 1.
5. The method for synthesizing triazine polyurethane charring agent containing furan ring side group as claimed in claim 2, wherein the molar ratio of the triazine diol or diamine containing furan ring side group, diisocyanate and diol chain extender in step 3) is (0.8-1.5) to 1 (0.05-0.5).
6. The method for synthesizing triazine based polyurethane charring agent containing furan ring pendant group as claimed in claim 2, wherein the triazine compound in step 1) is one or more of cyanuric chloride, cyanuric acid, trithiocyanuric acid and derivatives thereof.
7. The method of claim 2, wherein the furan ring-containing compound of step 1) is one or more of furancarbinol, furaldehyde, furylamine, furancarboxylic acid, furanmethylacetate, furfuryl thiol, and glycidylfurfuryl ether.
8. The method for synthesizing the triazine polyurethane charring agent containing the furan ring side group as claimed in claim 2, wherein the acid binding agent in the steps 1) and 2) is at least one of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium ethoxide, ethylenediamine, triethylamine and pyridine, preferably one of triethylamine and pyridine.
9. The method of claim 2, wherein the diamine or diol of step 2) is one or more of phenolphthalein, ethylene glycol, butylene glycol, ethylenediamine, butylene glycol, 4-diaminodiphenylmethane, and 4, 4-diaminodiphenylsulfone.
10. The method for synthesizing the triazine based polyurethane char-forming agent containing pendant furan ring groups of claim 2, wherein the diisocyanate in step 3) is one or more mixtures of diisocyanates having molecular weights less than 300 g/mol; the catalyst is an organic tin compound; the dihydric alcohol chain extender is at least one of ethylene glycol, propylene glycol and butanediol or a mixed chain extender of other polyhydric alcohol compounds.
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CN115093541B (en) * 2022-07-21 2023-07-21 马鞍山寅丰新材料科技有限公司 Stadium paving material based on polyurethane elastomer and preparation method thereof

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